Application of Oleochemicals in Paintings, Plastics, Textile and other Industries

Ahmad Mustafa

R&D and Quality Manager, Oleo Misr

ahmedm@oleomisr.com

www.oleomisr.com

Focus Points

Paints Industry.

Functionality of Oils!!

Plastics Industry.

Textile Industry.

Candles Industry.

Conclusion

• Today, water based paints are utilized higher that solvent based paints

Solvent Based

Relatively Long Drying Time

Release VOC.

Excellent Durability

Water Based

Quick Drying Time

Environmentally friendly

Excellent Durability

• Today, water based paints are utilized higher that solvent based paints

Alkyd coatings are a class of polyester coatings derived from thereaction of an alcohol (alkohol) and an acid or acid anhydride hencethe term alk-yd from “alcohol‘’

Reactants

Poly Basic Organic i.e. Phthalic

Polyoli.e. Glycerin

Fatty Acid or Triglyceride i.e. (soybean / Oleic Acid)

• Alkyd is polyester resin made from polybasic acid and polyhydricalcohol.

• Phthalic anhydride and Pentaerythitol are the most common di basicacid and polyol used in alkyd production.

Alkyd coatings are produced in two processesnamely fatty acid process and the alcoholysis orglyceride process.

Higher quality higher performance alkyds areproduced in the fatty acid process where thecomposition of the resulting resin can be moreprecisely controlled.

More economical alkyd resins are produced from thealcoholysis or glyceride process where end productquality control is not as paramount.

• Today, solvent-based paints (Alkyd Based)account for roughly 90% of paints sold inthe middle east and Africa markets for thepurpose of paining of steel, doors,widows,…etc. .

• Replacing solvent-borne alkyd with water-borne alkyd would not only reduce solventvapor emission but also improve safetyagainst the fire and health hazards oforganic solvents which undoubtedlycontinue to keep alkyds as major players inthe coatings area.

Percent PhthalicAnhydride

Percent Fatty AcidPercent OilAlkyd Resin Class(Oil Length)

< 20> 6856 > 70Long Oil

30 - 3543 - 5245- 55Medium Oil

> 35< 42< 45Short Oil

alkyd resins are classified by their oil length. For an alkydresin, the oil length is defined as the weight percent of oilor triglyceride equivalent, or alternatively, as the weightpercent of fatty acids in the finished resin,

In Egypt, Long and Medium alkyd resin account of about70% of total alkyd used.

Drying: depending on the ability of their film todry by air oxidation. This drying ability is derivedfrom the polyunsaturated fatty acids in the resincomposition. If drying oils, such as linseed oil, arethe sources of the fatty acids for the alkyd, theresin would belong to the drying type and isusually used as the film former of coatings or inks.

Nondrying: On the other hand, if the fatty acidscome from nondrying oils, such as coconut oil, theresin would be a nondrying alkyd. They are usedeither as plasticizers for other film-formers, suchas in nitrocellulose lacquers, or are cross-linkedthrough their hydroxyl functional groups tobecome part of the film former.

More frequently, an alkyd resin is classified by the sourceof the fatty acids, e.g., a linseed alkyd, a tung oil-modified soy alkyd, palm alkyd, Palm Kernel alked and acoconut alkyd.

Fatty AcidsOils

Reaction time is shorterLong Reaction Time

The reaction is selectiveRandom

Less Energy ConsumptionHigh Energy Consumption

more yellowing resistanceGives alkyd that has less yellowing resistance

More gloss retention Less gloss retention

Oils and polyol are not soluble in each other, that is why oils must beconverted to monoglycerines which performs a good emulsification.

However when oils reacts with polyol gives monoglycerides,diglycerinds, triglycerides, fatty acids and glycerin which gives arandom reaction mixture has an obligated amount of glycerin.

The common challenge for palm based alkyd resins are thatit is not able to air dry due to their low iodine value 56.

In order to overcome these problems, the use of alkydemulsions had been employed by emulsifying the alkyd resinsin water and by copolymerizing it with other monomer toenhance their properties or to interesterification with oil toproduce a workable resin product10

Printed Materials using Palm Oil Based Inks

• There has been a clear trend of gradual decline in themarket share of alkyd resins. However, their versatilityand low cost will undoubtedly continue to keep alkyds asmajor players in the coatings area.

• Great strides in the development of water-borne alkydshave also been made in recent years and it is expected tohas a very important effect in the future market of alkyds.

• a significant portion of the alkyds raw material, fattyacids, is renewable unlike the water based paints whichare depending totally on petroleum source.

• Oleomisr Company offers a high quality and cost advantagefatty acids to be used instead of oils in the alkyd industry.

• Oleomisr R&D department is giving attention to offer a newnatural local polyol to compete with Pentaerythitol .

• Oleomisr R&D department is giving attention to offer a naturalreplacer to Phthalic acid.

• The key petrochemicals for polymersynthesis(ethylene, propylene, styrene,vinyl chloride monomer, and others).

• These synthetic polymers are often notenvironmentally friendly because theytypically do not undergo the process ofbiodegradation.

• Dependent on a limited petroleumresource.

• Oils and fats are significant startingmaterials for the production ofbiodegradable and renewable polymer.

Functionality

Carbon-Carbon Double Bonds

Epoxy Group

Hydroxyl Groups

• The Major oils that contain carbon-carbon double bondsas the functional groups, linseed, corn, cottonseed,rapeseed, and soybean.

• These oils are called ‘‘drying oils,’’ which are defined asliquid oils that dry in air to form a solid film and aremore widely used as polymeric sources.

• The drying power of such oils is directly related to thechemical reactivity conferred on the TAG molecules bythe carbon-carbon double bonds of the unsaturatedacids, which allows them to react with atmosphericoxygen, thus leading to the process of polymerization toform polymeric networks.

Carbon-carbon double bond

Carbon-carbon double bond i.e. Synthesis of Thermoset Polyester

Polyesters Based Oleochemicals demonstrated physical properties similarto HDPE and therefore are also potential new degradable analogues oflinear polyethylene commodity plastics.

• Castor oil from castor beans containshigh percentage triacylglycerols (TAGs)of ricinoleic acid (83.6–90%), which is aC-18 fatty acid.

• Castor oil is unique in that its TAGscontain both double bonds andnonconjugated hydroxyl groups. The trifunctional nature of castor oil contributetoughness to the structure, and the longfatty acid chain imparts flexibility. As aresult of its unusual structure, this oil isvery versatile in its applications. It isused in making paints, adhesives, andurethane foams.

Hydroxyl Group Castor (The Magic Oil)

• The presence of the hydroxyl groups in the oils play an important role in polyurethane synthesis.

• Palm Oil can be coveted to polyol by epoxidationfollowed by alcoholysis.

• Oils such as Castor has a non conjugated hydroxyl group in its nature.

i.e. Polyurethane

Epoxy Group

• Vernonia oil contains a naturally occurring epoxide groupon C12. It is, therefore, important for the productions ofpolymers.

• Epoxidized soybean and linseed oils are the two mainrepresentatives of the industrially produced epoxidizedvegetable oils. Both are obtained by epoxidation of thecorresponding unsaturated oils, and the degree ofepoxidation can be controlled by reaction time.

Epoxidized soybean oil and palm oil are widely applied as a plasticizer instead of DEHP and DOP

with polyvinyl chloride (PVC) to improve PVC processing, stability, and flexibility.

• Textiles are produced from natural and synthetic fibers.

• Fibers have to go through a series of processes such asspinning, weaving, and dyeing.

• Fibers and yarns coming into contact with other surfacesundergo frictional, heating and abrasive damage andoften break, impairing the efficiency of the process.

• To overcome these problems, combinations of oils, fats,and their derivatives are used extensively as lubricantsand antistatic agents.

When two solid surfaces are pressed together with a force acting normal to them, they make points of contact, these points of contact form adhesive junctions.

• Adhesion of the lubricant film to the solid surface is an important requirement.

• Lack of adhesion will lead to the squeezing of the lubricant film out of the interface

• and the re-establishment of the solid–solid junctions

Fiber Lubrication

• Adhesion between the filaments of a yarn is an importantrequirement in processing of fibers. Twist contributessignificantly to yarn cohesion.

• Liquid bridges are formed by the applied finish, and• the capillary pressure of these liquid bridges is responsible for

the increase in cohesion.

• It is important to note that the presence of liquid bridges inthe yarn makes significant contribution to the strength of theyarn

Fiber Adhesion

• Although natural oils can be used as lubricants andprocessing aids in textiles, they have some seriousdrawbacks. As a result of unsaturation, these moleculesadsorb strongly on fiber surfaces and are not completelywashed off the finished goods.

• The residues form resinous products by autoxidation in thepresence of oxygen leading to ‘‘yellowing’’.

Natural Vs. Synthetic Oils

• Spinning is a major part of the textile industry It is part of the textile manufacturing process where fibres are converted into yarn,

• The commercial importance of spin finishes can be realized from the volume of synthetic fibers produced.

Spinning

• Mineral oils of different viscosity are used in the spinning of natural and synthetic fibers. These are paraffins of varying molecular weights, byproducts of the petroleum industry.

• Apart from lubricants, spin finishes contain antistaticand spreading and emulsifying agents. These aregenerally alkyl sulfates, fats and oils and poly(ethyleneglycol)-modified fatty acids, fatty acid amides, fattyalcohols, and fatty amines are extensively used in theproduction of polyester staple fibers.

i.e. oleochemicals in textile (names) butyl stearateSpinning

• Here oils and fats are used principally as detergents and wettingagents in the cleaning of natural fibers, to remove, for example, fatsand waxes from cotton and wool and in removing finishes used asprocessing aids in the manufacture of synthetics.

• Generally, anionic surfactants are used in this process. As mostnatural and synthetic fibers have negative charges on the surfaces,anionics will not adsorb strongly and therefore can be rinsed outeasily.

• Among the nonionic surfactants, alkyl, alkylphenol, fatty acid, andfatty-acid-amide-modified POEs are more common.

• The pH of the bath is an important consideration in the selection ofthe proper surfactants.

Scouring

In dyeing, surfactants are used as wetting agents. They are also used in theformulation of disperse dyes. A stable suspension of the dye is preparedwith the help of an anionic surfactant, such as alkyl or aryl alkyl sulfonate.

It has been shown that dyeing takes place through the aqueous phase bythe slow dissolution of the solid dye particles. The presence of thesurfactant helps the dissolution of the dye.

Dyeing

• Softening finishes are among the most important of textilechemical after treatments.

• With chemical softeners, textiles can achieve an agreeable,soft hand, some smoothness, more flexibility and better drapeand pliability.

Future Expansion

Laboratory

Softening

• Natural vegerable oils (unmodified) are susceptiple togegradation from oxidation and hydrolysis. To improvetheir oxidative and hydrolytic stability, as well as lowtemperature properties, they can be converted into esters.Typical examples include monoesters such as butylstearate and 20ethylhexyl palmitate, dibasic esters such asdi-isodecyl adipate and di-octyl sebacate and polyol esterssuch as trimethylolpropane esters.

• Palm oil and esters derived from it possess desirableproperties such as good adhesion to metal, good lubricity,strong oxidative stability and the right viscosity index.

Even through making the candles appears easy and simple, thesuccess of candles making involves many factors; one of themost important of which is the raw materials used.

Traditionally, bees wax and solid fats were used, however thelatter has always been objectionable because pyrolysis of thefats produces acrolein.

The delining use of bees wax is mainly due to its high price.

With the deveiopment of fat splitting, replacment of the solid fatby fatty acids has elimatned the accolyin problem.

With the increse in petroluem production, paraffin wax hasbecome the most important wax for candles because of itscompatitve price. But there are several problems ofparafin wax such as it produces smoke and its color is dull,doesn’t dissolve dyes and making demoulding diffecult.

One way to overcome these problems is to incorporate stearicacid. it is hard, has high contraction, disperses dyes easily,reflects light very well and imparts good lustre and

opacity.

Thank You

Ahmad Mustafa

R&D and Quality Manager, Oleo Misr

ahmedm@oleomisr.com

www.oleomisr.com